KR101786313B1 - Polyolefin composite composition for automotive airduct - Google Patents

Polyolefin composite composition for automotive airduct Download PDF

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KR101786313B1
KR101786313B1 KR1020160032291A KR20160032291A KR101786313B1 KR 101786313 B1 KR101786313 B1 KR 101786313B1 KR 1020160032291 A KR1020160032291 A KR 1020160032291A KR 20160032291 A KR20160032291 A KR 20160032291A KR 101786313 B1 KR101786313 B1 KR 101786313B1
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polyolefin
polyolefin composite
resin
weight
foamed
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KR1020160032291A
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KR20170108426A (en
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이슬
안부연
김대식
장경훈
한인수
박유진
남병국
이형신
김현진
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현대자동차주식회사
롯데케미칼 주식회사
기아자동차주식회사
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Priority to KR1020160032291A priority Critical patent/KR101786313B1/en
Priority to US15/284,782 priority patent/US9809691B2/en
Priority to CN201610915262.XA priority patent/CN107200899B/en
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Abstract

본 발명은 자동차 발포에어덕트에 사용되는 폴리올레핀 복합재 조성물에 관한 것으로, 더욱 상세하게는 폴리에틸렌 수지와 결정화도가 45% 이하로 낮은 고용융장력 폴리프로필렌 수지가 기재수지로 포함된 조성물로서 기계적 물성, 내열성 및 발포 특성이 모두 우수하여 자동차 발포에어덕트 부품 소재로 유용한 폴리올레핀 복합재 조성물에 관한 것이다.
The present invention relates to a polyolefin composite composition for use in automobile foamed air ducts, and more particularly, to a composition comprising a polyethylene resin and a high melt strength polypropylene resin having a crystallinity of 45% or less as a base resin and having mechanical properties, The present invention relates to a polyolefin composite composition useful as an automobile foamed air duct component material.

Description

자동차 발포에어덕트에 사용되는 폴리올레핀 복합재 조성물 {POLYOLEFIN COMPOSITE COMPOSITION FOR AUTOMOTIVE AIRDUCT}[0001] POLYOLEFIN COMPOSITE COMPOSITION FOR AUTOMOTIVE AIRDUCT [0002]

본 발명은 자동차 발포에어덕트에 사용되는 폴리올레핀 복합재 조성물에 관한 것으로, 더욱 상세하게는 폴리에틸렌 수지와 결정화도가 45% 이하로 낮은 고용융장력 폴리프로필렌 수지가 기재수지로 포함된 조성물로서 기계적 물성, 내열성 및 발포 특성이 모두 우수하여 자동차 발포에어덕트 부품 소재로 유용한 폴리올레핀 복합재 조성물에 관한 것이다.
The present invention relates to a polyolefin composite composition for use in automobile foamed air ducts, and more particularly, to a composition comprising a polyethylene resin and a high melt strength polypropylene resin having a crystallinity of 45% or less as a base resin and having mechanical properties, The present invention relates to a polyolefin composite composition useful as an automobile foamed air duct component material.

자동차에 탑재된 공조장치(Air Conditioning System)는 기후나 주행조건의 변화에도 차량에 탑승한 승객에게 쾌적한 환경을 제공하는 기능을 갖는다. 이러한 자동차의 공조장치에 있어서, 송풍되는 공기는 공기의 이송 통로가 되는 에어덕트를 따라 이동되고, 상기 에어덕트의 일단에 연결된 에어 벤트를 통해 자동차 실내로 송풍된다.The air conditioning system installed in the vehicle has a function of providing a pleasant environment to the passengers who ride in the vehicle even when the weather or driving conditions change. In the air conditioner of such an automobile, air to be blown is moved along an air duct which is a conveyance passage of air, and is blown into an automobile room through an air vent connected to one end of the air duct.

자동차의 공조장치용 에어덕트는 통상적으로 폴리에틸렌 수지를 블로우 몰딩 성형하여 제조된다. 그러나, 폴리에틸렌을 성형하여 제조한 솔리드 타입의 에어덕트는 밀도가 커서 자동차의 경량화에 저해요소가 되고 있다.BACKGROUND OF THE INVENTION Air ducts for air conditioners in automobiles are usually manufactured by blow molding molding a polyethylene resin. However, the solid type air duct manufactured by molding polyethylene has a large density, which is an obstacle to the weight reduction of automobiles.

또한, 솔리드 타입의 에어덕트는 단열성이 불량하여 수분의 응축 현상이 발생하며 자동차의 냉난방 효율을 저하시키므로, 이산화탄소 배출량을 증가시켜 자동차의 연비가 불량해진다. 이에 따라 솔리드타입의 에어덕트의 바깥 부분에는 부직포를 부착하여 단열성 향상과 함께 노이즈를 저감시키고 있으나, 중량에 따른 문제점이 여전히 존재하고, 제조공정도 추가되는 한계가 있다.In addition, solid type air ducts are poor in heat insulation and condensation phenomenon occurs, which lowers the cooling and heating efficiency of automobiles, resulting in an increase in carbon dioxide emissions, resulting in poor fuel efficiency of automobiles. Accordingly, the non-woven fabric is attached to the outer portion of the solid-type air duct to improve the heat insulation and reduce the noise. However, there is still a problem depending on the weight, and the manufacturing process is also limited.

이러한 문제점을 해결하기 위하여, 발포제로 발포되어 가볍고 단열성이 우수한 발포체를 에어덕트에 적용하려는 연구가 지속되어왔다. 그러나, 이러한 발포성 에어덕트는 발포체를 구성하는 수지 종류의 한계로 인하여, 원하는 경도를 얻을 수 없어, 기계적 물성이 양호한 에어덕트를 제조하기 어렵고, 최종 생산된 에어덕트의 표면 품질이 불량한 한계가 있었다.In order to solve such a problem, researches have been continued to apply foams that are foamed with a foaming agent and are light and excellent in heat insulation to air ducts. However, such a foamable air duct has a limitation in that it can not obtain desired hardness due to the limitation of the resin constituting the foam, and it is difficult to produce an air duct having good mechanical properties, and the surface quality of the air duct produced finally is poor.

또한, 한국공개특허 10-2015-0143199호(특허문헌 1)에는 112 ~ 150 ℃의 결정화 온도를 갖는 폴리프로필렌 수지, 저밀도 폴리에틸렌 수지, 무기필러 및 올레핀계 고분자를 포함하여 발포시킨 에어덕트 성형품이 개시되어 있다. 상기 특허문헌 1에서는 시차주사열량계(DSC)로 측정된 결정화온도가 112 ~ 150 ℃인 폴리프로필렌 수지를 기재에 포함시켜 빠른 표면고도화를 통해 성형품 제조시에 표면에서 발포셀이 터지는 현상을 최소화할 목적으로 포함시키고 있다. 하지만, 특허문헌 1에 의하면 폴리프로필렌 수지와 무기필러간의 상용성 문제로 물성 저하현상이 일어날 수 있으므로, 상용화제로서 올레핀계 고분자를 필수성분으로 포함시켜야 하는 단점이 있다.
Korean Patent Laid-open Publication No. 10-2015-0143199 (Patent Document 1) discloses an air duct molded article comprising a polypropylene resin, a low-density polyethylene resin, an inorganic filler and an olefin-based polymer having a crystallization temperature of 112 to 150 ° C . In Patent Document 1, a polypropylene resin having a crystallization temperature of 112 to 150 ° C. measured by differential scanning calorimetry (DSC) is included in a substrate to minimize the phenomenon of foaming cell popping on the surface during the production of a molded product through rapid surface enhancement . However, according to Patent Document 1, there is a disadvantage that an olefin-based polymer must be included as an essential component as a compatibilizer because physical properties may be lowered due to a compatibility problem between a polypropylene resin and an inorganic filler.

한국공개특허 10-2015-0143199호Korean Patent Publication No. 10-2015-0143199

본 발명에서는 상용화제를 첨가하지 않고도 기계적 물성, 내열성 및 발포 특성이 모두 우수한 폴리올레핀 복합재 조성물을 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a polyolefin composite composition excellent in mechanical properties, heat resistance and foaming properties without adding a compatibilizing agent.

또한, 본 발명은 상기한 폴리올레핀 복합재 조성물을 발포 성형한 자동차 발포에어덕트 성형품을 제공하는 것을 다른 목적으로 한다.
Another object of the present invention is to provide an automobile foamed air duct molded article obtained by foam-molding the above-mentioned polyolefin composite material composition.

상기한 과제 해결을 위하여, 본 발명은 폴리에틸렌 수지 65 내지 94.5 중량%; 결정화도가 20 ~ 45%인 고용융장력 폴리프로필렌 수지 5 내지 30 중량%; 및 무기필러 0.5 내지 5 중량%; 를 포함하는 폴리올레핀 복합재 조성물을 제공한다.In order to solve the above-mentioned problems, the present invention provides a resin composition comprising 65 to 94.5% by weight of a polyethylene resin; 5 to 30% by weight of a high melt tension polypropylene resin having a crystallinity of 20 to 45%; And 0.5 to 5% by weight of an inorganic filler; ≪ RTI ID = 0.0 > polyolefin < / RTI >

또한, 본 발명은 상기 조성물을 혼합한 후에 압출하여 제조된 폴리올레핀 복합재를 제공한다.The present invention also provides a polyolefin composite material prepared by mixing the above composition and then extruding it.

또한, 본 발명은 상기 폴리올레핀 복합재를 성형하여 제조된 자동차용 발포에어덕트 성형품을 제공한다.
The present invention also provides a foamed air duct molded article for automobile manufactured by molding the polyolefin composite material.

도 1은 (A)실시예 1 및 (B)비교예 1에서 제조된 발포시편을 광학 현미경으로 촬영한 사진이다.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph of the foamed specimen prepared in (A) Example 1 and (B) Comparative Example 1, taken under an optical microscope;

이하, 발명의 구체적인 구현예에 의해 폴리올레핀 복합재 조성물, 상기 조성물을 압출하여 제조된 폴리올레핀 복합재, 상기 복합재를 성형하여 제조된 발포에어덕트 성형품에 대해 보다 상세히 설명하기로 한다. 다만, 이는 발명의 하나의 예시로서 제시되는 것으로, 이에 의해 발명의 권리범위가 한정되는 것은 아니며, 발명의 권리범위 내에서 구현 예에 대한 다양한 변형이 가능함은 당 업자에게 자명하다.Hereinafter, a polyolefin composite material composition, a polyolefin composite material prepared by extruding the composition, and a foamed air duct molded product produced by molding the composite material will be described in detail with reference to specific embodiments of the present invention. It will be apparent to those skilled in the art, however, that this is not intended to limit the scope of the invention, which is presented as an illustration of the invention, and that various modifications to the embodiments are possible within the scope of the invention.

추가적으로, 본 명세서 전체에서 특별한 언급이 없는 한 "포함" 또는 "함유"라 함은 어떤 구성 요소(또는 구성 성분)를 별다른 제한 없이 포함함을 지칭하며, 다른 구성 요소(또는 구성 성분)의 부가를 제외하는 것으로 해석될 수 없다.
In addition, throughout this specification, "comprising" or "containing ", unless specifically stated, refers to including any and all components (or components) Can not be interpreted as excluding.

본 발명은 폴리에틸렌 수지, 결정화도가 20 ~ 45%인 고용융장력 폴리프로필렌 수지 및 무기필러를 포함하는 폴리올레핀 복합재 조성물을 제공한다.The present invention provides a polyolefin composite composition comprising a polyethylene resin, a high melt tension polypropylene resin having an crystallinity of 20 to 45%, and an inorganic filler.

폴리프로필렌 수지와 무기필러가 포함된 발포용 복합재의 경우 발포 특성이 열악하여 발포셀의 크기가 크고 발포셀 크기 편차가 심한 단점이 있으며, 이를 극복하기 위해 상용화제를 필수성분으로 포함하고 있다. 하지만, 본 발명에서는 결정화도가 45% 이하인 고용융장력 폴리프로필렌 수지(long chain branched PP)를 포함시킴으로써 별도로 상용화제를 포함하지 않고도 기계적 물성 및 내열성이 우수하면서도 발포 특성이 개선된 복합재 조성물을 제공하는 것이 가능하다.In the case of a foamed composite material containing a polypropylene resin and an inorganic filler, the foaming characteristics are poor, and the size of the foamed cell is large and the size of the foamed cell is disadvantageously large, and a compatibilizer is included as an essential ingredient to overcome this problem. However, the present invention provides a composite material having improved mechanical properties and heat resistance and improved foaming properties without including a compatibilizing agent separately by including a long chain branched PP having a crystallinity of 45% or less It is possible.

본 발명에 다른 폴리올레핀 복합재 조성물의 구성성분에 대해 보다 구체적으로 설명하면 다음과 같다.The constituent components of the polyolefin composite composition according to the present invention will be described in more detail as follows.

(1) 폴리에틸렌 수지(1) Polyethylene resin

본 발명의 복합재 조성물에는 폴리에틸렌 수지로서 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 선형저밀도폴리에틸렌(LLDPE), 및 에틸렌비닐아세테이트(EVA)로 이루어진 그룹에서 선택된 1종 이상이 포함될 수 있다.The composite material of the present invention may contain at least one selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ethylene vinyl acetate (EVA) as the polyethylene resin.

또한, 폴리에틸렌 수지는 용융지수가 0.5 ~ 10 g/10분 (230 ℃, 2.16 Kgf)인 폴리에틸렌 수지인 것이 사용될 수 있다. 폴리에틸렌 수지의 용융지수가 0.5 g/10분 (230 ℃, 2.16 Kgf) 미만이면 성형가공성이 저하될 수 있고, 반면에 용융지수가 10 g/10분 (230 ℃, 2.16 Kgf)을 초과하면 발포에어덕트의 두께 균일성에 문제점이 있을 수 있다.The polyethylene resin may be a polyethylene resin having a melt index of 0.5 to 10 g / 10 min (230 DEG C, 2.16 Kgf). If the melt index of the polyethylene resin is less than 0.5 g / 10 min (230 캜, 2.16 Kgf), the molding processability may be deteriorated. If the melt index exceeds 10 g / 10 min (230 캜, 2.16 Kgf) There may be a problem in the uniformity of the thickness of the duct.

상기 폴리에틸렌 수지는 본 발명의 폴리올레핀 복합재 조성물 중에 65 내지 94.5 중량%의 함량비로 포함될 수 있다. 만약 폴리에틸렌 수지의 함량이 65 중량% 미만이면 성형성에 문제가 있을 수 있고, 94.5 중량%를 초과하면 내열성에 문제가 있을 수 있다.
The polyethylene resin may be contained in the polyolefin composite composition of the present invention in a content ratio of 65 to 94.5% by weight. If the content of the polyethylene resin is less than 65% by weight, there may be a problem in moldability. If the content is more than 94.5% by weight, heat resistance may be a problem.

(2) 고용융장력 폴리프로필렌 수지(2) High melt tension polypropylene resin

본 발명의 복합재 조성물에는 폴리프로필렌 수지로서 결정화도가 45% 이하, 구체적으로는 결정화도가 20 ~ 45%인 고용융장력 폴리프로필렌 수지가 사용될 수 있다. 폴리프로필렌 수지의 결정화도가 45% 이하로 낮으면 발포성이 향상되는 효과를 기대할 수 있지만, 반면에 결정화도가 45%를 초과할 경우 결정화도가 높아 발포성이 저하될 수 있다.In the composite composition of the present invention, a high-melt-strength polypropylene resin having a crystallization degree of 45% or less, specifically, a crystallization degree of 20 to 45% may be used as the polypropylene resin. If the degree of crystallinity of the polypropylene resin is as low as 45% or less, an effect of improving foaming properties can be expected. On the other hand, when the degree of crystallization exceeds 45%, the degree of crystallization is high.

또한, 상기 고용융장력 폴리프로필렌 수지는 선형의 폴리프로필렌에 탄소수 2 ~ 100개의 긴 가지사슬(long chain branch)이 결합되어 있어, 용융시 높은 용융장력을 나타낸다. 이러한 고용융장력 폴리프로필렌 수지는 가지사슬이 4개/1,000C 이상, 구체적으로는 4 ~ 20개/1,000C 결합된 가지화된 폴리프로필렌 수지(long chain branched PP)를 사용할 수 있다. 즉, 폴리프로필렌 수지에 가지사슬이 결합되어 용융장력이 높아짐으로써 발포과정에서 셀이 붕괴되는 것을 막아주고 그리고 균일한 발포셀이 형성되도록 하는 효과를 얻을 수 있다. 그러나, 선형의 폴리프로필렌에 결합된 가지사슬의 개수가 4개/1,000C 미만일 경우는 용융장력이 낮아져서 균일한 발포셀을 구성할 수 없게 된다. 또한, 선형의 폴리프로필렌에 결합된 가지사슬의 개수가 20개/1,000C를 초과하면 용융장력이 지나치게 높아서 가공성이 저하되는 문제가 있다.In addition, the high melt tension polypropylene resin has a long chain branch of 2 to 100 carbon atoms bonded to a linear polypropylene and exhibits a high melt tension upon melting. Such a high melt tension polypropylene resin may use a long chain branched PP resin having 4 branch chains / 1,000C or more, specifically 4 to 20 / 1000C. That is, the polypropylene resin is combined with the branch chains to increase the melt tension, thereby preventing the cells from collapsing in the foaming process and forming a uniform foaming cell. However, when the number of branch chains bonded to the linear polypropylene is less than 4 / 1,000C, the melt tension is lowered and a uniform foam cell can not be formed. If the number of branch chains bonded to the linear polypropylene exceeds 20 / 1000C, the melt tension is excessively high and the processability is deteriorated.

또한, 고용융장력 폴리프로필렌 수지는 녹는점이 폴리에틸렌보다 높기 때문에 최종 성형품의 내열성을 향상시키는 효과도 기대할 수 있다.In addition, since the melting point polypropylene resin has a melting point higher than that of polyethylene, the effect of improving the heat resistance of the final molded article can be expected.

상기 고용융장력 폴리프로필렌 수지는 본 발명의 폴리올레핀 복합재 조성물 중에 5 내지 30 중량%의 함량비로 포함될 수 있다. 만약 고용융장력 폴리프로필렌 수지의 함량이 5 중량% 미만이면 발포 및 성형성에 문제가 있을 수 있고, 30 중량%를 초과하면 경제성 및 흐름성에 문제가 있을 수 있다.
The high melt tension polypropylene resin may be contained in the polyolefin composite composition of the present invention at a content ratio of 5 to 30% by weight. If the content of the high melt strength polypropylene resin is less than 5% by weight, there is a problem in foamability and moldability. If the content is more than 30% by weight, economical efficiency and flowability may be problematic.

(3) 무기필러(3) Inorganic fillers

상기 무기필러는 강성 보강 및 발포성 향상을 위해 사용되는 성분으로, 이의 선택에 특별히 제한을 두지 않는다. 무기필러는 구체적으로 탈크, 탄산칼슘, 황산칼슘, 산화마그네슘, 칼슘스테아레이트, 월라스토나이트, 마이카, 실리카, 규산칼슘, 점토, 휘스커 및 카본 블랙으로 이루어진 군으로부터 선택된 1종 이상이 사용될 수 있다. 무기필러의 사용은 함량 증가에 따라 수지 조성물의 강성 및 경도의 증가가 뚜렷한 것이 바람직한데, 대표적으로 월라스토나이트 또는 휘스커를 사용하는 것이 보다 바람직할 수 있다. The inorganic filler is a component used for reinforcing rigidity and improving foamability, and there is no particular limitation on the selection thereof. As the inorganic filler, at least one selected from the group consisting of talc, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, wollastonite, mica, silica, calcium silicate, clay, whisker and carbon black may be used. The use of the inorganic filler is preferably such that the stiffness and hardness of the resin composition increase with increasing content, and it is more preferable to use wollastonite or whisker.

본 발명의 복합재 조성물에 포함되는 무기필러의 평균 입경은 0.5 ~ 10 ㎛인 것이 바람직하며, 더욱 바람직하게는 1 ~ 4 ㎛인 것을 사용할 수 있다. 무기필러의 평균 입경이 0.5 ㎛ 미만이면 폴리올레핀 복합재의 생산성에 문제가 있을 수 있으며, 평균입경이 10 ㎛을 초과하면 폴리올레핀 복합재의 발포특성을 저하시킬 수도 있다.The average particle diameter of the inorganic filler contained in the composite composition of the present invention is preferably 0.5 to 10 mu m, more preferably 1 to 4 mu m. If the average particle diameter of the inorganic filler is less than 0.5 탆, the productivity of the polyolefin composite material may be problematic. If the average particle diameter exceeds 10 탆, the foam characteristics of the polyolefin composite material may be deteriorated.

상기 무기필러는 본 발명의 폴리올레핀 복합재 조성물 중에 0.5 내지 5 중량%의 함량비로 포함될 수 있다. 만약 무기필러의 함량이 0.5 중량% 미만이면 발포 기핵 작용에 문제가 있을 수 있고, 5 중량%를 초과하면 용융장력이 저하되는 문제가 있을 수 있다.
The inorganic filler may be contained in the polyolefin composite composition of the present invention at a content ratio of 0.5 to 5% by weight. If the content of the inorganic filler is less than 0.5% by weight, there may be a problem in the nucleating action of the foaming agent, while if it exceeds 5% by weight, the melt tension may be deteriorated.

(4) 첨가제(4) Additives

본 발명의 폴리올레핀 복합재 조성물은 폴리에틸렌 수지, 고용융장력 폴리프로필렌 수지 및 무기필러 이외에도 당분야에서 통상적으로 사용되고 있는 첨가제를 포함할 수 있다. 상기 첨가제는 구체적으로 산화방지제, UV안정제, 난연제, 착색제, 가소제, 열안정제, 슬립제, 대전방지제 등으로 이루어진 군으로부터 선택된 1 종 이상일 수 있다.The polyolefin composite composition of the present invention may contain additives conventionally used in the art in addition to polyethylene resin, high melt tension polypropylene resin and inorganic filler. The additive may specifically be at least one selected from the group consisting of an antioxidant, a UV stabilizer, a flame retardant, a colorant, a plasticizer, a heat stabilizer, a slip agent, and an antistatic agent.

상기 첨가제의 사용량은 각각 폴리올레핀 복합재를 제조하는 데 사용 가능한 것으로 알려진 범위 내에서 전체 제조량 및 제조 공정 등을 고려하여 최적 범위로 조절하여 사용할 수 있다. 그럼에도 불구하고 첨가제의 함량을 한정한다면 폴리올레핀 복합재 조성물 100 중량부를 기준으로 0.01 내지 10 중량부 범위내에서 사용될 수 있다.The amount of the additive to be used may be adjusted to an optimum range in consideration of the total production amount and the manufacturing process within a range known to be usable for producing the polyolefin composite material. Nevertheless, if the content of the additive is limited, it may be used within the range of 0.01 to 10 parts by weight based on 100 parts by weight of the polyolefin composite composition.

또한, 상기 첨가제는 폴리에틸렌 수지, 고용융장력 폴리프로필렌수지 및 무기필러를 혼합하는 단계에서 추가로 첨가할 수 있으며, 별도의 추가 단계로 혼련하여 첨가할 수도 있다.
Further, the additive may be added at the stage of mixing the polyethylene resin, the high melt tension polypropylene resin and the inorganic filler, or may be kneaded in a separate additional step.

한편, 본 발명은 상기한 폴리올레핀 복합재 조성물을 압출하여 제조된 폴리올레핀 복합재를 제공한다. 구체적으로 폴리에틸렌 수지, 고용융장력 폴리프로필렌 수지 및 무기필러를 혼합한 후에, 이 혼합물을 이축이상의 압출기에서 용융 압출시켜서 폴리올레핀 복합재로 제조될 수 있다. Meanwhile, the present invention provides a polyolefin composite material produced by extruding the above-mentioned polyolefin composite material composition. Specifically, a polyethylene resin, a high melt tension polypropylene resin, and an inorganic filler may be mixed, and then the mixture may be melt-extruded in an extruder having two or more coils to produce a polyolefin composite.

상기 용융 압출 단계는 스크류 회전 속도 200 ~ 1000 rpm의 조건 하에서 체류시간 5 ~ 90 sec으로 수행될 수 있으며, 바람직하게는 스크류 회전 속도 300 ~ 800 rpm의 조건 하에서 체류시간 10 ~ 60 sec으로 수행될 수 있다. 이때, 압출기 내부에서 수지간 혼련 및 무기필러 분산에 필요한 전단흐름(Shear flow) 및 신장흐름(Elongational flow)을 효과적으로 유도하기 위해서는 스크류 회전 속도는 200 rpm 이상이 되도록 하고, 폴리올레핀 수지의 열화 방지 측면에서 스크류 회전 속도는 1,000 rpm 미만이 바람직하다. 또한, 폴리에틸렌 수지, 고용융장력 폴리프로필렌 수지 및 무기필러가 충분히 혼련되기 위해서는 압출기 내부 체류시간은 5 sec 이상이 되어야 하고, 열화 방지 및 생산성 향상을 위해 체류시간은 90 sec 미만되어야 한다. The melt extrusion step may be carried out at a screw rotation speed of 200 to 1000 rpm under a retention time of 5 to 90 seconds and preferably at a screw rotation speed of 300 to 800 rpm for a retention time of 10 to 60 seconds have. In order to effectively induce the shear flow and the elongational flow necessary for kneading the resin in the extruder and dispersing the inorganic filler, the screw rotation speed is set to be 200 rpm or more, and in order to prevent deterioration of the polyolefin resin The screw rotating speed is preferably less than 1,000 rpm. In order to sufficiently knead the polyethylene resin, the high melt tension polypropylene resin and the inorganic filler, the residence time in the extruder should be 5 sec or more, and the residence time should be less than 90 sec in order to prevent deterioration and improve the productivity.

또한, 상기 용융 압출 단계의 온도가 160 ~ 200 ℃일 수 있다. 상기 용융 압출 온도가 160 ℃ 미만이면 복합재 조성물을 용융시키기 어려워서 복합재의 생산에 어려움이 있을 수 있고, 상기 용융 압출 온도가 200 ℃를 초과하면 폴리에틸렌 수지 및 고용융장력 폴리프로필렌 수지가 열화될 염려가 있다.In addition, the temperature of the melt extrusion step may be 160 to 200 ° C. If the melt extrusion temperature is less than 160 캜, it may be difficult to melt the composite composition and thus the composite material may be difficult to produce. If the melt extrusion temperature exceeds 200 캜, the polyethylene resin and the high melt tension polypropylene resin may deteriorate .

본 발명이 제공하는 폴리올레핀 복합재는 ASTM 평가법 D790에 의한 굴곡탄성율은 5,000 kg/㎠ 이상, 바람직하게는 12,000 kg/㎠ 이상이다. ASTM 평가법 D638에 의한 인장강도는 100 kg/㎠ 이상, 바람직하게는 200 kg/㎠ 이상이다. ASTM 평가법 D648에 의한 열변형온도는 60 ℃ 이상, 바람직하게는 90 ℃ 이상이 될 수 있다. 본 발명에 있어서 상기 기재된 내용 이외의 사항은 필요에 따라 가감이 가능한 것이므로, 본 발명에서는 특별히 한정하지 아니한다.
The polyolefin composites provided by the present invention have a flexural modulus of 5,000 kg / cm2 or more, preferably 12,000 kg / cm2 or more according to the ASTM Evaluation Method D790. The tensile strength according to the ASTM evaluation method D638 is 100 kg / cm2 or more, preferably 200 kg / cm2 or more. The heat distortion temperature according to the ASTM evaluation method D648 may be 60 占 폚 or higher, preferably 90 占 폚 or higher. In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

한편, 본 발명은 상술한 바와 같은 방법으로 제조되는 폴리올레핀 복합재를 이용하여 성형한 발포에어덕트 성형품을 제공한다. 상기 발포에어덕트는 자동차 내/외장용 소재로서, 자동차의 공조시스템 등에 적용될 수 있다. On the other hand, the present invention provides a foamed air duct molded article formed by using the polyolefin composite material produced by the above-described method. The foamed air duct can be applied to an automobile air conditioning system or the like as a material for an automobile interior / exterior.

구체적으로, 폴리올레핀 복합재에 발포제를 첨가하고 통상적으로 알려진 성형 방법으로 성형하여 발포에어덕트 성형품을 제조할 수 있다. 상기 발포에어덕트 성형품은 기재수지 내에 평균 직경이 20 ~ 50 ㎛인 발포셀이 균일하게 분포되어 있다.Specifically, a foaming agent may be added to the polyolefin composite material and molded by a conventionally known molding method to produce a foamed air duct molded article. In the foamed air duct molded article, foam cells having an average diameter of 20 to 50 mu m are uniformly distributed in the base resin.

상기 발포제는 폴리올레핀 수지의 발포 성형에 사용되는 물질을 일컫는 것으로 본 발명에서는 이의 선택에 특별한 제한을 두지 않는다. 다만, 폴리에틸렌 수지, 고용융장력 폴리프로필렌 수지의 종류와 특성, 용도, 가공방법, 조건 등에 따라 화학적 발포제, 물리적 발포제 등을 고려하여 당업자가 적절히 선택하여 사용할 수 있다. 상기 발포제로는 구체적으로 아조디카본아마이드, N,N'-디니트로소펜타메틸렌 테트라아민, p,p'-옥시비스(벤젠설포닐 하이드라지드), 5-페닐테트라졸, p-톨루엔설포닐 하이드라지드, 이산화탄소, 질소가스 또는 탄산수소나트륨 등이 포함될 수 있다.The foaming agent refers to a material used for foaming molding of a polyolefin resin, and there is no particular restriction on the selection of the foaming agent in the present invention. However, those skilled in the art can appropriately select and use the polypropylene resin and the high-melt-strength polypropylene resin in consideration of the types and properties of the polypropylene resin, the chemical foaming agent, and the physical foaming agent depending on the application, processing method and conditions. Specific examples of the foaming agent include azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, p, p'-oxybis (benzenesulfonylhydrazide), 5-phenyltetrazole, p- Carbon tetrachloride, phosphorus hydrazide, carbon dioxide, nitrogen gas or sodium bicarbonate, and the like.

상기 발포제의 함량 역시 발포제의 발포능력 등을 고려하여 당업자가 적절히 선택할 수 있다. 상기 발포제는 폴리에틸렌 수지와 고용융장력 폴리프로필렌 수지로 구성되는 폴리올레핀 기재수지 100 중량부를 기준으로 1 내지 10 중량부, 바람직하기로는 2 내지 5 중량부 범위로 첨가될 수 있다. 상기 발포제의 첨가량이 1 중량부 미만이면 폴리올레핀 기재상에 분포하는 발포셀이 충분히 형성되지 못하여 최종 폴리올레핀 수지 성형품의 단열성이 확보되기 어렵고, 10 중량부를 초과하면 발포셀이 지나치게 형성되어 오히려 성형품의 기계적 물성을 저하시킬 수 있다.The content of the foaming agent can also be appropriately selected by those skilled in the art in consideration of the foaming ability of the foaming agent. The foaming agent may be added in an amount of 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of a polyolefin based resin composed of a polyethylene resin and a high melt tension polypropylene resin. If the addition amount of the foaming agent is less than 1 part by weight, the foamed cells distributed on the polyolefin substrate can not be sufficiently formed, so that the heat insulating property of the final polyolefin resin molded article is difficult to secure. If the amount exceeds 10 parts by weight, the foamed cells are formed excessively, Can be reduced.

상기 성형 방법의 일 예로는 블로우 성형법을 들 수 있으며, 본 발명에서는 폴리올레핀 복합재의 성형방법에 대해 특별히 제한을 두지 않는다.
One example of the molding method is a blow molding method. In the present invention, the molding method of the polyolefin composite material is not particularly limited.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[실시예]
[Example]

실시예 1 ~ 2 및 비교예 1 ~ 3.Examples 1 to 2 and Comparative Examples 1 to 3.

하기 표 1에 나타낸 조성비로 폴리에틸렌 수지, 고용융장력 폴리프로필렌 수지 및 탈크를 혼합하였다. 상기 혼합물을 이축 압출기(스크류 직경 30 mm, L/D 40)에 넣은 다음, 160~200 ℃의 온도에서 용융시키면서 400 rpm의 스크류 회전속도 로 35 sec 동안 블렌딩하여 폴리올레핀 복합소재를 제조하였다. 상기 폴리올레핀 복합소재 100 중량부를 기준으로 추가로 발포제 3 중량부를 혼합한 후, 발포사출 성형기를 이용하여 시편 성형을 하였다.
Polyethylene resin, high melt tension polypropylene resin and talc were mixed in the composition ratios shown in Table 1 below. The mixture was placed in a biaxial extruder (screw diameter 30 mm, L / D 40) and blended at a screw rotation speed of 400 rpm for 35 seconds while melting at a temperature of 160 to 200 ° C to prepare a polyolefin composite material. 3 parts by weight of a foaming agent was further mixed based on 100 parts by weight of the polyolefin composite material, and then the specimen was molded using a foam injection molding machine.

[조성성분][Composition composition]

(1) 폴리에틸렌 수지(1) Polyethylene resin

(1-1) 고밀도폴리에틸렌: 용융지수가 2 g/10분이고, 밀도가 0.94 g/㎤인 폴리에틸렌 수지    (1-1) High-density polyethylene: A polyethylene resin having a melt index of 2 g / 10 min and a density of 0.94 g / cm 3

(1-2) 저밀도폴리에틸렌: 용융지수가 5 g/10분이고, 밀도가 0.92 g/㎤인 폴리에틸렌 수지    (1-2) Low density polyethylene: A polyethylene resin having a melt index of 5 g / 10 min and a density of 0.92 g / cm 3

(2) 고용융장력 폴리프로필렌 수지(2) High melt tension polypropylene resin

(2-1) 고용융장력 폴리프로필렌 수지: 결정화도 40%이고, 가지사슬이 평균 10개/1,000C 결합된 가지화된 폴리프로필렌 수지    (2-1) High-melt-strength polypropylene resin: a blend of branched polypropylene resin with an average degree of crystallization of 40% and branch chains of 10 / 1000C

(2-2) 고용융장력 폴리프로필렌 수지: 결정화도 53%이고, 가지사슬이 평균 10개/1,000C 결합된 가지화된 폴리프로필렌 수지    (2-2) High-melt tension polypropylene resin: a branched polypropylene resin having a degree of crystallinity of 53% and an average branch chain of 10 / 1000C

(3) 무기필러(3) Inorganic fillers

탈크: 평균직경 3 ㎛
Talc: average diameter 3 탆

[실험예][Experimental Example]

상기 실시예 1 ~ 2 및 비교예 1 ~ 3에서 제조된 폴리올레핀 복합재 발포시편의 물성을 하기의 방법으로 측정하였으며, 그 결과는 하기 표 1에 정리하여 나타내었다.The properties of the polyolefin composite foams prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following methods. The results are summarized in Table 1 below.

1) 기계적 특성1) Mechanical properties

① 인장강도(항복): ASTM 평가법 D638에 따라 인장강도를 측정하였다.Tensile strength (yield): The tensile strength was measured according to ASTM D638.

② 굴곡탄성율: ASTM 평가법 D790에 따라 굴곡탄성율을 측정하였다. Flexural Modulus: Flexural modulus was measured according to ASTM Evaluation Method D790.

③ IZOD 충격강도: ASTM 평가법 D256에 따라 23 ℃에서 IZOD 충격강도를 측정하였다. ③ IZOD impact strength: IZOD impact strength was measured at 23 캜 according to ASTM evaluation method D256.

2) 내열성 2) Heat resistance

ASTM 평가법 D648에 따라 열변형 온도를 측정하였다. The heat distortion temperature was measured according to ASTM Evaluation Method D648.

3) 발포 특성3) Foaming characteristics

광학현미경을 이용하여 1x1cm 범위에서 발포셀의 평균 직경 측정하였다.
The average diameter of the foamed cells was measured in the range of 1 x 1 cm using an optical microscope.

구 분division 실시예Example 비교예Comparative Example 1One 22 1One 22 33

조성
(중량%)

Furtherance
(weight%) 고밀도폴리에틸렌High density polyethylene 7979 7979 9999 7979 7979 저밀도폴리에틸렌Low density polyethylene -- 1010 -- 2020 -- 고용융장력폴리프로필렌High melt tension polypropylene 결정화도 40%Crystallinity 40% 2020 1010 -- -- -- 결정화도 53%Crystallinity 53% -- -- -- -- 2020 탈크Talc 1One 1One 1One 1One 1One



물성



Properties 인장강도
(Kg/cm2)The tensile strength
(Kg / cm 2 ) 150150 140140 135135 9090 155155 굴곡탄성률
(Kg/cm2)Flexural modulus
(Kg / cm 2 ) 13,30013,300 12,00012,000 11,60011,600 7,1007,100 14,80014,800 IZOD충격강도
(kgcm)IZOD impact strength
(kgcm) 3333 3939 2727 2222 3030 열변형온도
(℃)Heat distortion temperature
(° C) 9797 9595 6262 5555 9999 발포셀 평균직경
(㎛)Average diameter of foam cell
(탆) 5050 3535 550550 120120 350350

상기 표 1에 의하면, 고용융장력 폴리프로필렌 수지(결정화도 40%)를 사용한 실시예 1 ~ 2의 시편은 기계적 특성, 내열성 및 발포 특성이 모두 우수함을 확인할 수 있다.According to the above Table 1, it is confirmed that the specimens of Examples 1 and 2 using the high-melt-strength polypropylene resin (crystallinity of 40%) are excellent in both mechanical properties, heat resistance and foaming properties.

이에 반하면, 비교예 1 ~ 2의 시편은 고용융장력 폴리프로필렌 수지를 포함하지 않은 복합소재로서 실시예 1 ~ 2의 시편에 대비하여 기계적 물성이 열악하였고, 내열성 및 발포 특성도 매우 낮다는 것을 확인할 수 있다.On the contrary, the specimens of Comparative Examples 1 and 2 are composite materials that do not contain a high-melt-strength polypropylene resin and have poor mechanical properties and heat resistance and foaming characteristics compared with the specimens of Examples 1 and 2 Can be confirmed.

비교예 3의 시편은 결정화도가 높은 고용융장력 폴리프로필렌 수지를 포함하는 복합소재로서 실시예 1 ~ 2의 시편에 대비하여 기계적 특성과 내열성은 거의 동일한 수준에 있지만, 발포 특성이 저조하다는 것을 확인할 수 있다.
The specimen of Comparative Example 3 is a composite material containing a high melt strength polypropylene resin having a high degree of crystallinity, and is comparable to the specimens of Examples 1 and 2 in mechanical properties and heat resistance, but the foam characteristics are poor have.

또한, 도 1의 (A)와 (B)에는 상기 실시예 1 및 비교예 1에 따라 제조된 폴리올레핀 복합재의 발포시편을 광학 현미경으로 촬영한 사진이 첨부되어 있다.1 (A) and 1 (B) are photographs of a foamed specimen of a polyolefin composite material produced according to Example 1 and Comparative Example 1, taken by an optical microscope.

도 1의 광학 현미경 사진을 비교해 보았을 때, 실시예 1의 시편(A)은 발포에어덕트 내에 크기가 작고 균일한 셀이 형성되어있는데 반하여, 비교예 1의 시편(B)은 불균일한 크기의 셀이 형성되어 있음을 알 수 있다.1, the specimen (A) of Example 1 has small and uniform cells formed in the foamed air duct, whereas the specimen (B) of Comparative Example 1 has a uniform size cell As shown in FIG.

Claims (8)

폴리에틸렌 수지 65 내지 94.5 중량%;
결정화도가 20 ~ 40%이고, 가지사슬이 평균 4 ~ 20개/1,000C 달린 고용융장력 폴리프로필렌 수지 5 내지 30 중량%; 및
무기필러 0.5 내지 5 중량%;
를 포함하는 발포용 폴리올레핀 복합재 조성물.
65 to 94.5% by weight of a polyethylene resin;
5 to 30% by weight of a high melt tension polypropylene resin having a crystallinity of 20 to 40% and an average chain length of 4 to 20 / 1,000C; And
0.5 to 5% by weight of an inorganic filler;
Wherein the foamed polyolefin composite material is foamed.
제 1 항에 있어서,
상기 폴리에틸렌 수지는 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 선형저밀도폴리에틸렌(LLDPE) 및 에틸렌비닐아세테이트(EVA)로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 발포용 폴리올레핀 복합재 조성물.
The method according to claim 1,
Wherein the polyethylene resin is at least one selected from the group consisting of high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and ethylene vinyl acetate (EVA).
제 1 항에 있어서,
상기 폴리에틸렌 수지는 용융지수가 0.5 ~ 10 g/10분 (230 ℃, 2.16 Kgf)인 것을 특징으로 하는 발포용 폴리올레핀 복합재 조성물.
The method according to claim 1,
Wherein the polyethylene resin has a melt index of 0.5 to 10 g / 10 min (230 DEG C, 2.16 Kgf).
삭제delete 제 1 항에 있어서,
상기 무기필러는 평균 입경이 1 ~ 4 ㎛인 것으로, 탈크, 탄산칼슘, 황산칼슘, 산화마그네슘, 칼슘스테아레이트, 월라스토나이트, 마이카, 실리카, 규산칼슘, 점토, 휘스커 및 카본 블랙으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 발포용 폴리올레핀 복합재 조성물.
The method according to claim 1,
The inorganic filler has an average particle diameter of 1 to 4 탆 and is selected from the group consisting of talc, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, wollastonite, mica, silica, calcium silicate, clay, whisker and carbon black And at least one selected from the group consisting of polyolefin and polyolefin.
제 1 항에 있어서,
산화방지제, UV안정제, 난연제, 착색제, 가소제, 열안정제, 슬립제 및 대전방지제로 이루어진 군으로부터 선택된 1 종 이상의 첨가제를 더 포함하는 것을 특징으로 하는 발포용 폴리올레핀 복합재 조성물.
The method according to claim 1,
Wherein the composition further comprises at least one additive selected from the group consisting of antioxidants, UV stabilizers, flame retardants, colorants, plasticizers, heat stabilizers, slip agents and antistatic agents.
제 1 항 내지 제 3 항, 제 5 항 및 제 6 항 중에서 선택된 어느 한 항의 조성물을 혼합한 후에 용융 압출하여 제조된 폴리올레핀 복합재.
A polyolefin composite produced by mixing the composition of any one of claims 1 to 3, 5, and 6, followed by melt extrusion.
제 7 항의 폴리올레핀 복합재에 발포제를 포함시켜 발포 성형하여 제조된 자동차용 발포에어덕트 성형품.A foamed air duct molded article for automobile produced by foaming the polyolefin composite material of claim 7 by including a foaming agent.
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